US4110363AExpiredUtility

Preparation of esters

61
Assignee: SHELL OIL COPriority: Mar 1, 1976Filed: Feb 3, 1977Granted: Aug 29, 1978
Est. expiryMar 1, 1996(expired)· nominal 20-yr term from priority
Inventors:Roger SheldonPeter Been
C07C 255/14C07C 255/41C07C 253/16C07C 253/14C07C 2601/02
61
PatentIndex Score
4
Cited by
6
References
29
Claims

Abstract

Certain carboxylic acid esters also containing a cyano group are prepared by reacting an acid halide, an aldehyde and a water soluble cyanide in the presence of a water-immiscible aprotic solvent and a macrocylic polyether catalyst.

Claims

exact text as granted — not AI-modified
We claim: 
     
       1. A process for the preparation of an ester of the formula ##STR5## wherein Ar represents a phenoxy substituted phenyl group and R an alkyl group optionally substituted by halophenyl or alkylphenyl or a cyclopropyl group optionally substituted by alkyl, halogen, isobutenyl, dichlorovinyl or dibromovinyl, which process comprises contacting an aromatic aldehyde of the formula ArC(O)H and a (cyclo)aliphatic aryl halide of the formula RC(O)Hal, in which formulas Ar and R have the same meaning as in the formula I and Hal represents a halogen atom having an atomic number from 9 to 53, inclusive, with water, a water-soluble cyanide, a substantially water-immiscible aprotic solvent and a macrocyclic polyether phase transfer catalyst containing a total of from 4 to 80 atoms and 14 to 28 ring atoms at least 4 of which are oxygen atoms and recovering the desired ester from the reaction mixture. 
     
     
       2. A process according to claim 1, in which the molar ratio of the amount of phase transfer catalyst to the amount of aromatic aldehyde of the formula ArC(O)H is from 1:5 to 1:500. 
     
     
       3. A process according to claim 1, which is conducted at a temperature in the range of from 10° to 50° C. 
     
     
       4. A process according to claim 1, in which the total amount of the water-soluble cyanide is dissolved in the water. 
     
     
       5. A process according to claim 4, in which the substantially water-immiscible aprotic solvent is a (cyclo)alkane or a mixture of (cyclo)alkanes. 
     
     
       6. A process according to claim 5, in which the alkane is n-heptane. 
     
     
       7. A process according to claim 5, in which the (cyclo)alkane is cyclohexane. 
     
     
       8. A process according to claim 1, which is conducted in the presence of solid water-soluble cyanide. 
     
     
       9. A process according to claim 8, in which the substantially water-immiscible aprotic solvent is an aromatic hydrocarbon or a mixture of aromatic hydrocarbons. 
     
     
       10. A process according to claim 9, in which the aromatic hydrocarbon is toluene. 
     
     
       11. A process according to claim 8, in which the substantially water-immiscible aprotic solvent is a chlorinated hydrocarbon. 
     
     
       12. A process according to claim 1, in which the starting molar ratio of the amount of water to the total amount of water-soluble cyanide is higher than 0.05. 
     
     
       13. A process according to claim 12, in which the starting molar ratio of the amount of water to the total amount of water-soluble cyanide is in the range of from 0.05 to 1. 
     
     
       14. A process according to claim 1, in which the molar ratio of the amount of (cyclo)aliphatic acyl halide of the formula RC(O)Hal to the amount of the aromatic aldehyde of the formula ArC(O)H is in the range of from 1.1 to 1.0. 
     
     
       15. A process according to claim 14, in which the molar ratio of the amount of (cyclo)aliphatic acyl halide of the formula RC(O)Hal to the amount of the aromatic aldehyde of the formula ArC(O)H is 1.0. 
     
     
       16. A process according to claim 1, in which the water-soluble cyanide is sodium cyanide. 
     
     
       17. A process according to claim 1, in which Hal in the formula RC(O)Hal represents a chlorine atom. 
     
     
       18. A process according to claim 1, in which the group R in the formula RC(O)Hal is an optionally substituted (cyclo)alkyl group having a tertiary or quaternary carbon atom bound to the group --C(O)Hal. 
     
     
       19. A process according to claim 18, in which the group R is a 1-(4-chlorophenyl)-2-methylpropyl group or an isopropyl group. 
     
     
       20. A process according to claim 18, in which the group R is an optionally substituted cyclopropyl group. 
     
     
       21. A process according to claim 20, in which the group R is a 2,2,3,3-tetramethylcyclopropyl group or a 2-(2,2-dichlorovinyl)-3,3-dimethylcyclopropyl group. 
     
     
       22. A process according to claim 19, which is carried out by forming a mixture of the total amounts of the aromatic aldehyde, the (cyclo)aliphatic acyl halide, the water, the water-soluble cyanide and the substantially water-immiscible aprotic solvent, and stirring the mixture thus formed. 
     
     
       23. A process according to claim 21, which is carried out by gradual addition of a 2,2,3,3-teteramethylcyclopropanecarbonyl halide to a stirred mixture of the aromatic aldehyde, the water, the water-soluble cyanide and the substantially water-immiscible aprotic solvent. 
     
     
       24. A process according to claim 1, wherein the macrocyclic polyether catalyst is 1,4,7,10,13,16-hexaoxacyclooctadecane, 3,4-benzo-1,6,9,12,15,18,21-heptaoxacyclotricos-3-ene or 3,4-benzo-1,6,9,12-tetraoxacyclotetradec-3-ene. 
     
     
       25. A process according to claim 1 wherein the macrocyclic polyether catalyst contains 5 to 8 ring oxygen atoms. 
     
     
       26. A process according to claim 25 wherein the water soluble cyanide is sodium cyanide and the solvent is an alkane, a cycloalkane, an aromatic hydrocarbon, chlorinated hydrocarbon or a mixture thereof. 
     
     
       27. A process according to claim 26 which is conducted at a temperature in the range of from 10° C to 50° C, with the molar ratio of the amount of (cyclo)aliphatic acyl halide to the amount of the aromatic aldehyde is from 1.1 to 1.0 and in which the starting molar ratio of the amount of water to the total amount of water-soluble cyanide is higher than 0.05. 
     
     
       28. A process according to claim 27 wherein the macrocyclic polyether catalyst is 1,4,7,10,13,16-hexaoxacyclooctadecane, 3,4-benzo-1,6,9,12,15,18,21-heptaoxacyclotricos-3-ene or 3,4-benzo-1,6,9,12-tetraoxacyclotetradec-3-ene. 
     
     
       29. A process according to claim 28 wherein the ester of formula I is α-cyano-3-phenoxybenzyl 2-(4-chlorophenyl)-3-methylbutanoate.

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